Asymmetric Catalytic Hydrogenation with an Optically Active Phosphinerhodium Complex in Homogeneous Solution

Horner, L.; Siegel, Hardo; Büthe, H.

doi:10.1002/anie.196809422

Cited by 307 publications

(118 citation statements)

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“…This is reflected by the fact that papers and reviews have appeared at an ever increasing rate since the end of the 1960s, when the first papers using chiral metal catalysts were published by Knowles [26] and Horner [27]. Since then, the discoveries made by Noyori and Sharpless [28] have had a very great impact on academic research and the development of new drugs and materials, and they are used in many industrial syntheses of drugs and other biologically active compounds.…”

Section: Enantioselective Catalysismentioning

confidence: 99%

Metalloporphyrin Symmetry in Chiral Recognition and Enantioselective Catalysis

et al. 2014

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Symmetry plays a fundamental role in chiral recognition and enantioselective catalysis. Porphyrins possess a number of structural features that make them attractive for the stereocontrol of chiral recognition and metal-catalyzed asymmetric reactions. This article is a brief account of our studies on chiral recognition and enantioselective catalysis by optically active metalloporphyrins. Some of the studies on chiral recognition and asymmetric catalysis by metalloporphyrins performed by others have also been included when useful.

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Section: Enantioselective Catalysismentioning

confidence: 99%

Metalloporphyrin Symmetry in Chiral Recognition and Enantioselective Catalysis

et al. 2014

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“…These ligands were reacted with [RhCl(cod)] 2 , followed by treatment with NaBF 4 , to afford the corresponding rhodium cationic complexes 5a ± d as air-stable orange powders.…”

Section: Synthesis Of Optically Pure 12-bis[(oalkylphenyl)phenylphosmentioning

confidence: 99%

“…The enantiomeric excess of the product was determined to be 77% ee by HPLC analysis [DAICEL CHIRALPAK AS, hexane:2-propanol ¼ 9 : 1, 1.0 mL/min, (R) t 1 ¼ 7. 4 To a solution of (S)-o-methylphenyl(methyl)phenylphosphine-borane (77% ee) (1.30 g, 5.7 mmol) in THF (23 mL) was added sec-BuLi (6.5 mL of 0.96 mol/L cyclohexane solution) at À 78 8C with stirring. After 2 h, freshly dried, well-powdered anhydrous copper(II) chloride (1.15 g, 8.6 mmol) was added with vigorous stirring and the mixture was gradually warmed to room temperature over 2 h. After stirring for an additional 1 h, water and ethyl acetate were added and the mixture was passed through Celite.…”

Section: (S)-o-methylphenyl(methyl)phenylphosphine-borane (3b)mentioning

confidence: 99%

“…The enantiomeric excess of the product was determined to be 88% ee by HPLC analysis [DAICEL CHIRALCEL OJ, hexane:2-propanol ¼ 9 : 1, 1.0 mL/min, (R) t 1 ¼ 10. 4 A solution of (S)-o-ethylphenyl(methyl)phenylphosphineborane (90% ee) (324 mg, 1.34 mmol) was dissolved in THF (7 mL) was cooled to À 78 8C under argon. To this solution sec-BuLi (1.4 mL of 1.05 M/L cyclohexane solution) was added, and stirring was continued for 2 h. Freshly dried, well-powdered anhydrous copper(II) chloride (270 mg, 2.0 mmol) was added with vigorous stirring.…”

Section: Experimental Section General Proceduresmentioning

confidence: 99%

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Optically Pure 1,2‐Bis[(o‐alkylphenyl)phenylphosphino]ethanes and Their Use in Rhodium‐Catalyzed Asymmetric Hydrogenations of α‐(Acylamino)acrylic Derivatives

et al. 2004

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Optically pure (S,S)-1,2-bis[(o-alkylphenyl)-phenylphosphino]ethanes 1a ± d were prepared in four steps from phenyldichlorophosphine via phosphine-boranes as the intermediates. The rhodium complexes 5a ± d of these diphosphines were used for the asymmetric hydrogenations of a-(acylamino)-acrylic derivatives including b-disubstituted derivatives. Markedly high enantioselectivity (78 ± > 99%) was observed for the reduction of b-monosubstituted derivatives. b-Disubstituted derivatives were also reduced in considerably high enantioselectivity (up to 90%). The single crystal X-ray analysis of the rhodium complex 5c of (S,S)-1,2-bis[phenyl(5',6',7',8'-tetrahydronaphthyl)phosphino]ethane (1c) revealed its dtype structure with face orientation of the two tetrahydronaphthyl groups and edge orientation of the two phenyl groups. This conformation corresponds to that of the rhodium complex of 1,2-bis[(o-methoxyphenyl)phenylphosphino]ethane (DIPAMP); the rhodium complex of (R,R)-DIPAMP, whose chirality at phosphorus is opposite that of 5c, exhibits a l-type structure with the face orientation of the two o-methoxyphenyl groups and the edge orientation of the two phenyl groups. The conformational similarity of these rhodium complexes as well as the stereochemical outcome in the asymmetric hydrogenations means that the coordinative interaction of the methoxy group of DIPAMP with rhodium metal is not the main factor that affects asymmetric induction.

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“…The development of homogeneous catalysis using organometallic complexes in mid-sixties encouraged people to prepare chiral complexes for catalysis [2]. The first and modest results were obtained in 1961 for polymerization [3], in 1966 in cyclopropanation [4] and in 1968 in hydrogenation [5,6]. The asymmetric hydrogenation was especially promissing for applications.…”

Section: Introductionmentioning

confidence: 99%

Nonlinear Effects in Enantioselective Organometallic Catalysis

Kagan

2007

Oil & Gas Science and Technology - Rev. IFP

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*Dedicated to Yves Chauvin for his outstanding contributions to catalysis Ce manuscrit est dédié à Yves Chauvin pour ses contributions exceptionnelles à la catalyse Résumé -Effets nonlinéaires dans la catalyse organométallique énantiosélective -L'historique de la catalyse organométallique énantiosélective est rappelé en introduction. Les problèmes liés à l'emploi d'auxiliaires chiraux énantioimpurs sont discutés, les effets nonlinéaires sont définis et des modèles mathématiques simples sont présentés. De nombreux exemples d'effets nonlinéaires positifs ou négatifs sont maintenant connus, certains sont mentionnés. Les effets nonlinéaires sont utiles pour aborder des mécanismes réactionnels. L'amplification asymétrique peut avoir des applications en catalyse, en permettant d'utiliser un ligand qui n'est pas énantiopur. Abstract -Nonlinear Effects in Enantioselective Organometallic

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Asymmetric Catalytic Hydrogenation with an Optically Active Phosphinerhodium Complex in Homogeneous Solution

Cited by 307 publications

References 1 publication

Metalloporphyrin Symmetry in Chiral Recognition and Enantioselective Catalysis

Metalloporphyrin Symmetry in Chiral Recognition and Enantioselective Catalysis

Optically Pure 1,2‐Bis[(o‐alkylphenyl)phenylphosphino]ethanes and Their Use in Rhodium‐Catalyzed Asymmetric Hydrogenations of α‐(Acylamino)acrylic Derivatives

Nonlinear Effects in Enantioselective Organometallic Catalysis

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